Polymer thickened hair colouring and bleaching compositions

ABSTRACT

The present invention relates to hair colouring and hair bleaching compositions comprising a source of carbonate ions, at least one oxidizing agent and a specified polymer thickner wherein said composition is free of a source of radical scavengers. The compositions surprisingly provide improved hair colourant and bleaching compositions which deliver improved lift, lightening and colour delivery whilst minimizing damage which are easy to manufacture and have long shelf life stability.

FIELD OF THE INVENTION

The present invention relates to hair colourant and bleachingcompositions.

BACKGROUND OF THE INVENTION

The permanent alteration of the colour of keratinous fibres, inparticular human hair, by the application of hair dyes is well known. Inorder to provide the consumer with the hair colour and the intensity ofcolour desired, a very complex chemical process is utilized. Permanenthair dyeing formulations typically comprise oxidative hair dyeprecursors, which can diffuse into the hair through the cuticle and intothe cortex where they can then react with each other and suitableoxidising agents to form the end dye molecules. Due to the larger sizeof these resultant molecules they are unable to readily diffuse out ofthe hair during subsequent washing with water and/or detergents; hencedelivering a consumer-desired permanency of colour. This reactiontypically takes place in an aggressive environment at approximately pH10 in the presence of an alkalizing agent and in the presence of anoxidizing agent. Moreover, the consumer repeats this process regularlyin order to maintain the desired hair colour and shade and the intensityof colour and to ensure continual, even coverage of the hair includingcoverage of new hair growth.

The manufacturer of such products is also required to work within alarge number of constraints. Since these products are being placed indirect contact with the consumers' skin, the potential exists foraccidental contact with the eye or for ingestion (for example), whichcan occur during the dyeing process. Therefore, the formulation mustmeet rigorous safety requirements and not induce any allergic reactions.In addition to meeting these requirements, the products must also beoptically and olfactory pleasing to the consumer. In particular, theproducts also need to meet certain physical parameters in order toensure that the product can be easily applied to the hair by theconsumer to provide the desired effect, without unintentional stainingof the consumers' clothes, skin, particularly along the hair line, orother objects.

The manufacturer is also required to provide the hair colouring consumera large range of different resulting colours. Some consumers may justwish to enhance the natural colour of the hair, whilst others may wishto cover grey or completely alter the hair colour to a different naturalappearing hair colour or a ‘synthetic’ appearing hair colour.Consequently, the manufacturer may provide over twenty differentformulations, of varying colours and shades, to address the range ofconsumer specific needs. These formulations have to be individuallyformulated and are typically complex formulae containing a mixture ofdifferent dye compounds. As a result the manufacture of such productranges can be costly and complex.

However, despite the fact that commercial hair dyeing products have beenavailable for many years, the products still exhibit a number ofconsumer-related deficiencies.

Typically permanent hair dye products will contain an alkali, typicallya source of ammonia. This serves the purpose of swelling the hairallowing the entry of the dye precursor molecules into the hair and alsoimproves the lightening effect of the oxidising agent, which istypically hydrogen peroxide. However, ammonia is also volatile and itsassociated odour is extremely unpleasant to the consumers' of suchproducts, particularly as these hair dye products are used in closeproximity to the nasal region. Hence, it would be highly desirable toprovide an oxidative hair colouring and/or bleaching composition, whichdelivers the consumer required lightening level and colour, but whichhas reduced or eliminated the detectable ammonia odour.

In fact another deficiency area in current hair colouring products isthe provision of hair colouring products which deliver the required hairlightening effect. Delivering the required level of lightening isparticularly important in order to provide the full range of colourshades demanded by the consumer, especially for blonde shades and greycoverage. Such products pose particular difficulties to themanufacturer, as they usually require the use of high levels ofoxidising agent and ammonia in order to deliver the required lighteningeffect. However, in additional to the problems associated with thepresence of high levels of ammonia in these products, as discussedherein above, the presence of these high levels of ammonia and/oroxidizing agent also affect the condition of the hair and may in somecases induce mild skin irritation on the scalp. In particular, thehydrophilicity of the hair surface is increased during the colouringprocess, which alters the sensory perception of the hair and its overallmanageability during and, immediately after colouring, and during thesubsequent wash and styling cycles until the next colourant application.Hence, it would also be highly desirable to provide an oxidative haircolouring and/or bleaching composition which delivers the requiredlightening and/or colour without unnecessary hair damage.

A number of attempts have been described in the literature to address atleast some of the above identified improvement areas. For example theuse of carbonate has been described in the following hair colouring art.EP 435 012 describes hair-dyeing compositions, which require a shortdyeing time, create little damage to hair, and no irritating odour afterdyeing comprising a carbonate source, a non odour generating alkalihydrogen peroxide and a buffer solution. Similarly EP 1 106 166describes hair dye compositions comprising ammonia, carbonate (otherthan ammonia salt), transition metal salt and chelating agent which donot give off an irritating odour, have low skin irritation and canchange the hair colour into a lighter tone in a short time. WO01/28508describes hair colouring formulations comprising oxidising agents andammonia carbonate or carbamate which deliver improved bleaching andcolouring with reduced odour and hair damage without the need forbuffering agents, pH modifiers or hair swelling agents. JP01206825describes a low pungent hair colouring composition comprising ammonia,ammonium salt and carbonate. US2004/0083557 describes hair colouringcompositions comprising an oxidative hair dye precursor, a metalcyanate, an alkalizing agent and an oxidizing agent and preferably ametal bicarbonate salt in order to provide good colour lift and lowodour.

WO04/014328 describes one step hair colouring compositions comprisingperoxide oxidizing agents, specific oxidizing agents and at least onewater soluble carbonate releasing salts which more effectively delivercolour wherein the composition is applied for a period of from 2 to 60minutes. US2004/0098814 describes a method of permanently colouring hairwhereby the hair is subjected to a number of consecutive shorttreatments whereby the treatment comprises a dye intermediate in ashampoo or conditioner base, a water soluble carbonate releasing saltand a water soluble ammonium salt. US2004/0098816 also describes amethod for the gradual permanent colouring of hair which includessubjecting the hair to a number of treatments having a set time intervalbetween them, wherein the treatment compositions comprise ammoniumcarbonate in combination with a chelant.

However it has now been found that the use of hydrogen peroxide andcarbonate hair colourant systems, results in difficulties inmanufacturing. This problem is particularly manifest for compositionswhich have high levels of peroxide and carbonate which are desirable toprovide high levels of lift. Moreover in order to provide a productwhich the consumer can easily apply to the hair without dripping ontothe skin, clothes or bathroom surfaces, hair colourant products aredesigned such that the composition has a certain required viscosity.This is either achieved by providing the dye composition and theoxidizing composition as so called thin-thin type liquid formulationswhich are thickened upon mixing or where at least one of the components,either the dye composition or the oxidizing composition, preferably thedye composition, is provided as a thickened formulation which thickensthe total composition upon mixing.

Carbonate systems in the art herein above describe numerous materialssuitable for thickening. However these materials have been found not tosufficiently thicken compositions comprising high levels of carbonateresulting in product instability or unsatisfactory viscosity. Hence itwould be desirable to provide a hair colorant composition whichincorporates high levels of carbonate without compromising the productstability or ease of manufacture.

Another particularly critical performance area for the consumer is theprovision of the desired resultant colour and also the effectivecoverage of grey hair. Indeed, whilst the amount of grey hair to becoloured varies considerably from consumer to consumer, the resultantoverall appearance of the coloured hair demanded by the consumer shouldbe nearly identical for the naturally pigmented hair and the grey hairon head, with the added requirement that the initial uniform and evencolour coverage is maintained during the post dyeing washing and dryingcycle.

Hence, it would be further desirable to provide the consumer with a haircolourant, providing improved lift and lightening and improved colourdelivery, uptake and durability and which is easy to manufacture,delivering the required viscosity and is shelf life stable.

It has now been surprisingly found that oxidative hair colouringcompositions comprising an oxidising agent, a source of carbonate ions,a specific polymeric thickener as defined herein at pH 9.3 and below canbe formulated as stable thickened systems. Moreover the compositionsexhibit low odour and deliver a high level of lift and lightening equalto the currently utilised ammonia/peroxide systems, whilst reducing theconcentration of peroxide and reducing the hair fibre damage. Moreover,the compositions of the present invention are compatible with currentdyes and dye precursor systems and result in improved lift andlightening for blond shades, excellent dye deposition and colour andimproved grey coverage.

SUMMARY OF THE INVENTION

The present invention relates to a hair colouring or bleachingcomposition comprising

i) at least about 0.2 mol/l of a source of carbonate, carbamate,hydrogencarbonate ions, or peroxymonocarbonate ions and mixturesthereof,

ii) at least one oxidizing agent and

iii) at least one polymeric thickener selected from associativepolymers, non-associative polycarboxylic polymers, and mixtures thereof,

wherein said composition has a pH of up to and including about 9.3 andwherein said composition is free of a source of radical scavengers.

A further embodiment of the present invention relates to a haircolouring or bleaching kit comprising

i) an individually packaged oxidizing component comprising at least onesource of hydrogen peroxide

ii) an individually packaged liquid second component comprising

-   -   a) at least one polymeric thickener selected from associative        polymers, polysaccharides non-associative, polycarboxylic        polymers, and mixtures thereof, and    -   b) a source of carbonate ions, carbamate ions, hydrogencarbonate        ions, and    -   c) at least about 10% of a solvent, preferably water,        wherein said kit is free of a source of radical scavengers and        upon mixing said components comprises at least about 0.2 mol/l        of a source of carbonate ions, carbamate ions, hydrogencarbonate        ions or peroxymonocarbonate ions and mixtures thereof, except        when said polymeric thickener is an associative polymer when        said composition comprises at about least 0.4 mol/l of said        source.

An alternative embodiment relates to a hair colouring or bleaching kitcomprising

i) an individually packaged liquid oxidizing component comprising

-   -   a) at least one source of hydrogen peroxide, and    -   b) at least one polymeric thickener selected from associative        polymers, polysaccharides, non-associative polycarboxylic        polymers, and mixtures thereof, and    -   c) at least about 10% by weight of a solvent, preferably, water,        ii) an individually packaged second component comprising a        source of carbonate ions, carbamate ions or hydrogencarbonate        ions and mixtures thereof        wherein said kit is free of a source of radical scavengers and        upon mixing said components comprises at least about 0.2 mol/l        of a source of carbonate ions, carbamate ions, hydrogencarbonate        ions, peroxymonocarbonate ions and mixtures thereof, except when        said polymeric thickener is an associative polymer when said        composition comprises al least about 0.4 mol/l of said source.

A further embodiment relates to a method of colouring or bleaching haircomprising the steps of applying a composition comprising at least about0.2 mol/l of source of carbonate, carbamate, hydrogencarbonate ions orperoxymonocarbonate ions and mixture thereof, and at least one polymericthickener selected from associative polymers, polysaccharides,non-associative cross-linked polycarboxylic polymers, and mixturesthereof, wherein said composition is free of radical scavenger, to thehair.

In a further aspect the present invention relates to a method ofapplying the compositions of the present invention to the hair andleaving the compositions on the hair for up to about 60 minutes, andsubsequently rinsing the compositions from the hair.

Another aspect of the present invention relates to a method ofsequential oxidative hair colouring or hair bleaching comprising thesteps of at least two sequential oxidative hair colour or hair bleachingtreatments wherein the time period between each treatment is from about1 day to about 60 days, and wherein each treatment comprises the stepsof providing a composition of the present invention, then applying saidcomposition to the hair and retaining said composition on the hair for atime period of less than about 20 minutes and subsequently rinsing saidcomposition from the hair.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims, which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

As used herein the term “hair” to be treated may be “living” i.e. on aliving body or may be “non-living” i.e. in a wig, hairpiece or otheraggregation of non-living keratinous fibers. Mammalian, preferably humanhair is preferred. However wool, fur and other keratin containing fibersare suitable substrates for the compositions according to the presentinvention.

All percentages are by weight of the total composition unlessspecifically stated otherwise. When more than one composition are usedduring a treatment, the total weight to be considered is the totalweight of all the compositions applied on the hair simultaneously (i.e.the weight found “on head”) unless otherwise specified. All ratios areweight ratios unless specifically stated otherwise. All molarconcentrations are by volume of the total composition and presented asnumber of moles of component(s) in one litre of the composition, or“mol/l”. When more than one composition are used during a treatment, thetotal volume to be considered is the total volume of all thecompositions applied on the hair simultaneously (i.e. the volume found“on head”) unless otherwise specified.

Carbonate Ion Source

According to the present invention the compositions comprise at least0.2 mol/l of source of carbonate ions or carbamate ions orhydrogencarbonate ions or peroxymonocarbonate ions or any mixturethereof. This amount can be achieved for example by addition of at leastabout 1.92% (volume percent) of ammonium carbonate (molecular weightequals to 96.09 g/mol) to the composition of invention or, for example,by addition of about 1.0% (volume percent) of Ammonium Carbonate and atleast about 0.96% (volume percent) of Potassium Hydrogen Carbonate(molecular weight equals 100.12 g/mol). The compositions of the presentinvention preferably comprises from about 0.4 mol/l to about 2.0 mol/l,more preferably from about 0.5 mol/l to about 1.5 mol/l of the source ofsaid ions.

It should also be understood that when the composition of the inventionis used as a hair colouring or bleaching kit comprising and individuallypackaged oxidizing component and an individually packaged secondcomponent such as a bleaching or colouring component, the concentrationof the source of the said ions will be increased in the said bleachingor colouring component proportionally to the mixing ratio of componentsin order to achieve the concentration of at least 0.2 mol/l (or 0.4mol/l) upon mixing of the components to provide the composition appliedto the hair.

Any source of these ions may be utilized. Suitable sources for useherein include sodium, potassium, lithium, calcium, magnesium, barium,ammonium salts of carbonate, carbamate and hydrogencarbonate ions andmixtures thereof such as sodium carbonate, sodium hydrogen carbonate,potassium carbonate, potassium hydrogen carbonate, lithium carbonate,calcium carbonate, magnesium carbonate, barium carbonate, ammoniumcarbonate, ammonium hydrogen carbonate and mixtures thereof.Percarbonate salts may also be utilized to provide both the source ofcarbonate ions and oxidizing agent. Preferred sources of carbonate ions,carbamate and hydrogencarbonate ions are sodium hydrogen carbonate,potassium hydrogen carbonate, ammonium carbamate and mixtures thereof.

In a particularly preferred embodiment of the present invention, theammonium ion source and the carbonate ion sources are provided by asingle source such as ammonium carbonate, ammonium hydrogen carbonate,ammonium carbamate or mixtures thereof.

Oxidizing Agent

The compositions according to the present invention thus formperoxymonocarbonate ions. These ions are typically formed in-situ fromthe reaction between a source of hydrogen peroxide and carbonate ion.Consequently, the compositions according to the present inventioncomprise or are used in combination with a composition that comprises atleast one source of an oxidizing agent. Preferred oxidizing agents foruse herein are water-soluble peroxygen oxidizing agents. “Water-soluble”as defined herein means that in standard condition at least 0.1 g,preferably 1 g, more preferably 10 g of said oxidizing agent can bedissolved in 1 liter of deionized water. The oxidizing agents arevaluable for the initial solubilisation and decolorisation of themelanin (bleaching) and accelerate the oxidation of the oxidative dyeprecursors (oxidative dyeing) in the hair shaft.

Any oxidizing agent known in the art may be utilized in the presentinvention. Preferred water-soluble oxidizing agents are inorganicperoxygen materials capable of yielding hydrogen peroxide in an aqueoussolution. Water-soluble peroxygen oxidizing agents are well known in theart and include hydrogen peroxide, inorganic alkali metal peroxides suchas sodium periodate and sodium peroxide and organic peroxides such asurea peroxide, melamine peroxide, and inorganic perhydrate saltbleaching compounds, such as the alkali metal salts of perborates,percarbonates, perphosphates, persilicates, persulphates and the like.These inorganic perhydrate salts may be incorporated as monohydrates,tetrahydrates etc. Alkyl and aryl peroxides, and/or peroxidases may alsobe used. Mixtures of two or more such oxidizing agents can be used ifdesired. The oxidizing agents may be provided in aqueous solution or asa powder which is dissolved prior to use. Preferred for use in thecompositions according to the present invention are hydrogen peroxide,percarbonate (which may be used to provide a source of both oxidizingagent and carbonate ions), persulphates and combinations thereof.

According to the present invention the compositions comprise from about0.1% to about 10% by weight, preferably from about 1% to about 7% byweight, and most preferably from about 2% to about 5% by weight of anoxidizing agent.

Polymer Thickener

According to the present invention, the hair colouring and bleachingcompositions comprise a polymer thickener, comprising at least onepolymer selected from associative polymers, polysaccharides,non-associative polycarboxylic polymers, and mixtures thereof.

Those skilled in the art will recognize that polymer thickening systemsusually provide thickening by chain entanglement, network formation ormicro-gel swelling. These systems usually have gel appearance and feeland are thus strongly desirable.

However, polymer thickeners can be salted out by high level of carbonatesalts, leading to viscosity loss. Further, osmotic swelling of micro-gelparticles made of, for example, cross-linked polymers is suppressed bycarbonate salt addition, also resulting in viscosity loss.

Even further, other components of typical colouring composition such assolvents and oxidative or pre-formed dyes, affect polymer properties andmake selection of suitable polymers in carbonate systems particularlydifficult. Further, in one of the embodiment of this invention, polymershave to be incorporated into a liquid composition i.e a compositioncomprising at least 10% by weight of a solvent such as water, togetherwith carbonate salts, and provide shelf life stability of such liquidcomposition.

Surprisingly, it has now been found that by the required specificselection of the polymer thickener, thickening efficiency can beachieved. Without being bound by theory, it is believed that the polymerthickener described in this invention has sufficiently high molecularweight to resist salting-out by carbonate salts, or exhibits networkformation via hydrophobic associative groups not affected by thepresence of high concentrations of carbonate ions, or demonstratessufficient osmotic swelling of micro-gel particles due to specificselection of polymer hydrophilic monomers, thus providing sufficientthickening.

According to the present invention the hair coloring or bleachingcompositions and kits thereof comprise at least one polymeric thickenerselected from associative polymers, polysaccharides, non-associativecross-linked polycarboxylic polymers, and mixtures thereof.

As used herein, the expression “associative polymers” means amphiphilicpolymers comprising both hydrophilic units and hydrophobic units, forexample, at least one C8 to C30 fatty chain and at least one hydrophilicunit. Associative polymers are capable of reversibly combining with eachother or with other molecules. Representative associative thickenersthat may be used are associative polymers chosen from:

(i) nonionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit;

(ii) anionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit;

(iii) cationic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit; and

(iv) amphoteric amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit.

The nonionic amphiphilic polymers comprising at least one fatty chainand at least one hydrophilic unit may, for example, be chosen from:

(1) celluloses modified with groups comprising at least one fatty chain;for example: hydroxyethylcelluloses modified with groups comprising atleast one fatty chain chosen from alkyl, alkenyl and alkylaryl groups;

(2) hydroxypropyl guars modified with groups comprising at least onefatty chain;

(3) polyether urethanes comprising at least one fatty chain, such asC8-C30 alkyl or alkenyl groups;

(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobicmonomers;

(5) copolymers of C1-C6 alkyl acrylates or methacrylates and ofamphiphilic monomers comprising at least one fatty chain;

(6) copolymers of hydrophilic acrylates or methacrylates and ofhydrophobic monomers comprising at least one fatty chain.

The anionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit, may, for example, be chosen fromthose comprising at least one fatty-chain allyl ether unit and at leastone hydrophilic unit comprising an ethylenic unsaturated anionicmonomeric unit, for example, a vinylcarboxylic acid unit and further,for example, chosen from units derived from acrylic acids, methacrylicacids and mixtures thereof, wherein the fatty-chain allyl ether unitcorresponds to the monomer of formula below:CH2=C(R1)CH2OBnR  (I)in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n ischosen from zero and integers ranging from 1 to 100, R is chosen fromhydrocarbon-based radicals chosen from alkyl, alkenyl, arylalkyl, aryl,alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms,and, further, for example, from 10 to 24 carbon atoms and even further,for example, from 12 to 18 carbon atoms.

The anionic amphiphilic polymers may further be chosen, for example,from those comprising at least one hydrophilic unit of unsaturatedolefinic carboxylic acid type, and at least one hydrophobic unit of thetype such as a (C8-C30) alkyl ester or (C8-C30) oxyethylenated alkylester of an unsaturated carboxylic acid. The hydrophilic unit ofunsaturated olefinic carboxylic acid type corresponds to, for example,the monomer of formula (II) below:CH2=C(R1)COOH  (II)in which R1 is chosen from H, CH3, C2H5 and CH2COOH, i.e. acrylic acid,methacrylic, ethacrylic and itaconic acid units. And the hydrophobicunit of the type such as a (C8-C30) alkyl ester or (C8-C30)oxyethylenated alkyl ester of an unsaturated carboxylic acid correspondsto, for example, the monomer of formula (III) below:CH2=C(R1)COOBnR2  (III)in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylate,methacrylate, ethacrylate and itaconate units), B is an ethyleneoxyradical, n is chosen from zero and integers ranging from 1 to 100, R2 ischosen from C8-C30 alkyl radicals, for example, C12-C22 alkyl radical.

Representative anionic amphiphilic polymers that can be used may furtherbe cross-linked.

The crosslinking agent can be a monomer comprising a group (IV)CH2=C<  (IV)with at least one other polymerizable group whose unsaturated bonds arenot conjugated with respect to one another. Mention may be made, forexample, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

The cationic amphiphilic polymers used are, for example, chosen fromquaternized cellulose derivatives and polyacrylates comprising aminoside groups. The quaternized cellulose derivatives are, for example,chosen from quaternized celluloses modified with groups comprising atleast one fatty chain, such as alkyl, arylalkyl and alkylaryl groupscomprising at least 8 carbon atoms, and mixtures thereof, quaternizedhydroxyethylcelluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof. The alkyl radicals borne bythe above quaternized celluloses and hydroxyethylcelluloses, forexample, contain from 8 to 30 carbon atoms. The aryl radicals, forexample, are chosen from phenyl, benzyl, naphthyl and anthryl groups.

Among amphoteric amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit, mention may be made,for example, of methacrylamidopropyltrimethylammonium chloride/acrylicacid/C8-C30 alkyl methacrylate copolymers, wherein the alkyl radical is,for example, a stearyl radical.

Preferable associative polymeric thickeners for use herein comprise atleast one hydrophilic unit which is unsaturated carboxylic acid or itsderivative, and at least one hydrophobic unit which is a C8 to C30 alkylester or oxyethylenated C8-C30 alkyl ester of unsaturated carboxylicacid. The unsaturated carboxylic acid is preferably acrylic acid,methacrylic acid or itaconic acid. Examples can be made of material soldunder trade name Aculy-22 by the company Rohm & Haas, materials soldunder trade names Permulen TR1, Carbopol 2020, Carbopol Ultrez-21 by thecompany Noveon, and materials sold under the trade names Structure 2001and Structure 3001 by the company National Starch. Another preferableassociative polymer for use in the polymer thickening systems of thepresent invention include polyether polyurethane, for example materialssold under the trade name Aculyn-44 and Aculyn-46 by the company Rohmand Haas. Another preferable associative polymer for use herein iscellulose modified with groups comprising at least one C8-C30 fattychain, such as the product Natrosol Plus Grade 330 CS sold by thecompany Aqualon.

Non-associative cross-linked polycarboxylic polymers for use herein canbe chosen, for example, from:

(i) cross-linked acrylic acid homopolymers;

(ii) copolymers of acrylic or (meth)acrylic acid and of C1-C6 alkylacrylate or (meth)acrylate.

Preferable polymers are the products sold under the names Carbopol 980,981, 954, 2984, 5984 by the company Noveon or the products sold underthe names Synthalen M, Synthalen L and Synthalen K by the company 3VSigma, or the product sold under the name Aculyn-33 by the company Rohmand Haas.

The polysaccharides for use herein are, for example, chosen fromglucans, modified and unmodified starches (such as those derived, forexample, from cereals, for instance wheat, corn or rice, fromvegetables, for instance yellow pea, and tubers, for instance potato orcassaya), amylose, amylopectin, glycogen, dextrans, celluloses andderivatives thereof (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans,lignins, arabans, galactans, galacturonans, chitin, chitosans,glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acidsand pectins, alginic acid and alginates, arabinogalactans, carrageenans,agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums,karaya gums, carob gums, galactomannans, such as guar gums, and nonionicderivatives thereof (hydroxypropyl guar) and bio-polysaccharides, suchas xanthan gums, gellan gums, welan gums, scleroglucans, succinoglycansand mixtures thereof.

For example, suitable polysaccharides are described in “Encyclopedia ofChemical Technology”, Kirk-Othmer, Third Edition, 1982, volume 3, pp.896-900, and volume 15, pp. 439-458, in “Polymers in Nature” by E. A.MacGregor and C. T. Greenwood, published by John Wiley & Sons, Chapter6, pp. 240-328,1980, and in “Industrial Gums—Polysaccharides and theirDerivatives”, edited by Roy L. Whistler, Second Edition, published byAcademic Press Inc., the content of these three publications beingentirely incorporated by reference.

The polysaccharide is preferably a bio-polysaccharide, particualrypreferable are bio-polysaccharides selected from xanthan gum, gellangum, welan gum, scleroglucan or succinoglycan, for example material soldunder the name Keltrol® T by the company Kelco and the material sold bythe name Rheozan® by the company Rhodia Chimie.

Another preferable polysaccharide is hydroxypropyl starch derivative,particularly preferable hydroxypropyl starch phosphate, for example thematerial sold under the name Structure XL® by the company NationalStarch.

pH

The compositions of the present invention have a pH up to and includingabout pH 9.3. Preferably, the compositions of the present invention havea pH of from about 9.3 to about 7.5, more preferably from about 9.3 toabout 8.4 and most preferably from about 9.2 to about 8.5 and even morepreferably about pH 9.0. Preferably, the compositions of the presentinvention are prepared such that prior to application to the hair fibresthe pH of the composition is no greater than about pH 9.3. However, inanother embodiment of the present invention the compositions may beformulated such that the pH is up to 9.3 during the time period ofapplication of the composition to the hair fibres prior to removaltherefrom. Preferably, the pH is up to about 9.3 for at least about 50%of the time period, preferably at least about 70%, most preferably atleast about 80% of the time period of application of the composition tothe hair. More preferably, the pH of the composition is up to about pH9.3 within about 10 minutes, preferably within about 5 minutes ofapplication to the hair fibres.

The pH of the compositions can be determined by using either a MettlerToledo MP220 or a MP225 pH equipment, fitted with a standard laboratorypH electrode. The equipment is calibrated before each use using standardcalibration buffers and using standard calibration procedure.

Radical Scavenger

According to the present invention the compositions are typically freeof a source of radical scavenger. The term free as used herein refers tocompositions comprising less than 3%, preferably less than 2%, morepreferably less than 1%, even more preferably less than 0.1% even morepreferably less than 0.01% and even more preferably less than 0.001% andmost preferably substantially free of a source of radical scavenger.

As used herein the term radical scavenger refers to compounds accordingto the general formula: (I): R¹—Y—C(H)(R³)—R⁴—(C(H)(R⁵)—Y—R⁶)_(n)

wherein Y is NR², O, or S, preferably NR², n is 0 to 2, and wherein R⁴is monovalent or divalent and is selected from: (a) substituted orunsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (b) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (c) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; the systems of(a), (b) and (c) comprising from 1 to 12 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; and wherein R⁴ can beconnected to R³ or R⁵ to create a 5, 6 or 7 membered ring; and whereinR¹, R², R³, R⁵, and R⁶ are monovalent and are selected independentlyfrom: (a), (b) and (c) described herein above, or H.

Preferably, R⁴ is selected from: (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems, (b) substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems, or (c) substitutedor unsubstituted, mono-, poly-, or per-fluoro alkyl systems; morepreferably R⁴ is selected from (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, or heteroaliphaticsystems, (b) substituted or unsubstituted, aryl, or heterocyclicsystems, or (c) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; more preferably substituted or unsubstituted,straight or branched, alkyl, or heteroalkyl systems.

Preferably, the R⁴ systems of (a), (b), and (c), described herein above,comprise from 1 to 8 carbon atoms, preferably from 1 to 6, morepreferably from 1 to 4 carbon atoms and from 0 to 3 heteroatoms;preferably from 0 to 2 heteroatoms; most preferably from 0 to 1heteroatoms. Where the systems contain heteroatoms, preferably theycontain 1 heteroatom. Preferred heteroatoms include O, S, and N; morepreferred are O, and N; and most preferred is O.

Preferably, R¹, R², R³, R⁵, and R⁶ are selected independently from anyof the systems defined for R⁴ above, and H.

In alternative embodiments, any of R¹, R², R³, R⁴, R⁵, and R⁶ groups aresubstituted. Preferably, the substituent(s) is selected from: (a) thegroup of C-linked monovalent substituents consisting of: (i) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (ii) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (iii) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (i), (ii) and (iii) comprising from 1 to 10 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; (b) the group of S-linkedmonovalent substituents consisting of SA¹, SCN, SO₂A¹, SO₃A¹, SSA¹,SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²; (c) the group of O-linkedmonovalent substituents consisting of OA¹, OCN and ONA¹A²; (d) the groupof N-linked monovalent substituents consisting of NA¹A², (NA¹A²A³)⁺, NC,NA¹OA², NA¹SA², NCO, NCS, NO₂, N═NA¹, N═NOA¹, NA¹CN, NA¹NA²A³; (e) thegroup of monovalent substituents consisting of COOA¹, CON₃, CONA¹ ₂,CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and (f) the groupconsisting fluoroalkyl monovalent substituents consisting of mono-,poly-, or per-fluoro alkyl systems comprising from 1 to 12 carbon atomsand 0 to 4 heteroatoms.

For the groups (b) to (e), described above, A¹, A², and A³ aremonovalent and are independently selected from: (1) H, (2) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (3) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (4) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (2), (3) and (4) comprising from 1 to 10 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; and wherein X is a halogenselected from the group consisting of F, Cl, Br, and I.

Preferred substituents for use herein include those having a HammettSigma Para (σ_(p)) Value from −0.65 to +0.75, preferably from −0.4 to+0.5. Hammett Sigma Values are described in Advanced OrganicChemistry—Reactions, Mechanisms and Structure (Jerry March, 5^(th) ed.(2001) at pages 368-375). Without being limited by theory, it isbelieved that substituents having sigma para values in the chosenranges, when substituted onto R¹ and/or R2, may improve the compound'stoxicological profile without unduly adding an unfavourable increase inmolecular weight that may interfere with the molecule's ability topenetrate the hair shaft. Some preferred substituents and their HammettSigma Para values are shown below, in Table A. Additional substituentsand their values are shown in March, at page 370. TABLE A SubstituentNH₂ OH H COO— Cl COOH CF₃ □_(p) −0.57 −0.38 0 0.11 0.24 0.44 0.53

Preferably the above defined radical scavengers have a pKa of more than7 to prevent the protonation of the nitrogen.

Preferably the present invention further does not comprise radicalscavengers according to the general formula (II):

wherein R₁, R₂, R₃, R₄, and R₅ are each independently selected from H,COO⁻M⁺, Cl, Br, SO₃ ⁻M⁺, NO₂, OCH₃, OH or a C¹ to C¹⁰ primary orsecondary alkyl and M is either H or alkali metal. Preferably, theabove-described radical scavengers have a pKa of more than 8.5 to ensureprotonation of the hydroxy goup.

Preferably the present invention further also does not comprise radicalscavengers according to those selected from group (III) benzylamine,imidazole, di-tert-butylhydroxytoluene, hydroquinone, guanine, pyrazine,piperidine, morpholine, methylmorpholine, 2methyoxyethylamine, andmixtures thereof.

Even more preferably the present invention does not comprise radicalscavenger defined as a species that can react with a carbonate radicalto convert the carbonate radical by a series of fast reactions to a lessreactive species, i.e. a carbonate radical scavenger.

Whilst not being bound by theory, it is believed that the ability of theradical scavenger to convert the carbonate radical (as describedhereinabove) is dependant upon the energy of the charge transferreaction as shown below: (The calculation of the energy of the chargetransfer reaction is detailed hereinafter.)Scavenger+CO₃ ^(*−)→Scavenger^(*+)+CO₃ ²⁻wherein the energy of the reaction is defined by:—ΔH _(r) =ΔH _(f)(products)−ΔH _(f)(reactants)=ΔH _(f)(Scavenger^(*+))+ΔH_(f)(CO₃ ²⁻)−ΔH _(f)(Scavenger)−ΔH _(f)(CO₃ ^(*−))

According to the present invention the composition do not comprise aradical scavenger having an energy of reaction of from about 0 kcal/molto about 14 kcal/mol, preferably from about 1.5 kcal/mol to about 9kcal/mol.

Additional Components

The compositions of the present invention may further compriseadditional ingredients which include, but are not limited to, hairdyeing agents such as oxidative dye precursors, non-oxidative dyes,solvents, enzymes, surfactants, conditioning agents, carriers,antioxidants, stabilizers, chelants, perming actives, perfume, reducingagents (thiolactic acid), hair swelling agents and/or polymers. Some ofthese additional components are detailed hereafter.

Source of Alkalizing Agent

According to the present invention the composition may optionallycomprise at least one source of alkalizing agent, preferably a source ofammonium ions and or ammonia. Particularly, preferred alkalizing agentsare those which provide a source of ammonium ions. Any source ofammonium ions is suitable for use herein. Preferred sources includeammonium chloride, ammonium sulphate, ammonium nitrate, ammoniumphosphate, ammonium acetate, ammonium carbonate, ammonium hydrogencarbonate, ammonium carbamate, ammonium hydroxide, percarbonate salts,ammonia and mixtures thereof. Particularly preferred are ammoniumcarbonate, ammonium carbamate, ammonia and mixtures thereof. Preferably,if present, the ammonium ions and carbonate ions are present in thecomposition at a weight ratio of from 3:1 to 1:10, preferably 2:1 to1:5.

The compositions of the present invention may comprise from about 0.1%to about 10% by weight, preferably from about 0.5% to about 5%, mostpreferably from about 1% to about 3% of an alkalizing agent, preferablyammonium ions.

Hair Dyes

The hair compositions of the present invention are preferably haircolouring compositions which comprise oxidative dyeing compositions.Such compositions comprise oxidative hair dye precursors (also known asprimary intermediates) that will deliver a variety of hair colors to thehair. These small molecules are activated by the oxidizing agent andreact with further molecules to form a larger colored complex in thehair shaft.

The precursors can be used alone or in combination with otherprecursors, and one or more can be used in combination with one or morecouplers. Couplers (also known as color modifiers or secondaryintermediates) are generally colorless molecules that can form colors inthe presence of activated precursors, and are used with other precursorsor couplers to generate specific color effects or to stabilize thecolor. The choice of precursors and couplers will be determined by thecolor, shade and intensity of coloration that is desired. The precursorsand couplers can be used herein, singly or in combination, to providedyes having a variety of shades ranging from ash blonde to black.

These compounds are well known in the art, and include aromaticdiamines, aminophenols, aromatic diols and their derivatives (arepresentative but not exhaustive list of oxidation dye precursor can befound in Sagarin, “Cosmetic Science and Technology”, “Interscience,Special Edn. Vol. 2 pages 308 to 310). Suitable dyes for use hereininclude:—1,7-Dihydroxynaphthalene (1,7-NAPHTHALENEDIOL),1,3-Diaminobenzene (m-PHENYLENEDIAMINE), 1-Methyl-2,5-diaminobenzene(TOLUENE-2,5-DIAMINE), 1,4-Diaminobenzene (p-PHENYLENEDIAMINE),1,3-Dihydroxybenzene (RESORCINOL), 1,3-Dihydroxy-4-chlorobenzene,(4-CHLORORESORCINOL), 1-Hydroxy-2-aminobenzene, (o-AMINOPHENOL),1-Hydroxy-3-aminobenzene (m-AMINOPHENOL), 1-Hydroxy-4-amino-benzene(p-AMINOPHENOL), 1-Hydroxynaphthalene (1-NAPHTHOL),1,5-Dihydroxynaphthalene (1,5-NAPHTHALENEDIOL),2,7-Dihydroxy-naphthalene (2,7-NAPHTHALENEDIOL),1-Hydroxy-2,4-diaminobenzene (4-DIAMINOPHENOL), 1,4-Dihydroxybenzene(HYDROQUINONE), 1-Hydroxy-4-methylaminobenzene (p-METHYLAMINOPHENOL),6-Hydroxybenzo-morpholine (HYDROXYBENZOMORPHOLINE),1-Methyl-2-hydroxy-4-aminobenzene (4-AMINO-2-HYDROXY-TOLUENE),3,4-Diaminobenzoic acid (3,4-DIAMINOBENZOIC ACID),1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene(2-METHYL-5-HYDROXY-ETHYLAMINO-PHENOL), 1,2,4-Trihydroxybenzene(1,2,4-TRIHYDROXYBENZENE), 1-Phenyl-3-methylpyrazol-5-on (PHENYL METHYLPYRAZOLONE), 1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene(2,4-DIAMINOPHENOXY-ETHANOL HCL), 1-Hydroxy-3-amino-2,4-dichlorobenzene(3-AMINO-2,4-DICHLORO-PHENOL), 1,3-Dihydroxy-2-methylbenzene(2-METHYLRESORCINOL), 1-Amino-4-bis-(2′-hydroxyethyl)aminobenzene(N,N-BIS(2-HYDROXY-ETHYL)-p-PHENYLENE-DIAMINE),2,4,5,6-Tetraminopyrimidine (HC Red 16),1-Hydroxy-3-methyl-4-aminobenzene (4-AMINO-m-CRESOL),1-Hydroxy-2-amino-5-methylbenzene (6-AMINO-m-CRESOL),1,3-Bis-(2,4-Diaminophenoxy)propane(1,3-BIS-(2,4-DIAMINO-PHENOXY)-PROPANE),1-(2′-Hydroxyethyl)-2,5-diaminobenzene (HYDROXYETHYL-p-PHENYLENE DIAMINESULPHATE), 1-Methoxy-2-amino-4-(2′-hydroxyethylamino)benzene(2-AMINO-4-HYDROXY-ETHYLAMINOANISOLE),1-Hydroxy-2-methyl-5-amino-6-chlorobenzene (5-AMINO-6-CHLORO-o-CRESOL),1-Hydroxy-2-amino-6-methylbenzene (6-AMINO-o-CRESOL),1-(2′-Hydroxyethyl)-amino-3,4-methylenedioxybenzene(HYDROXYETHYL-3,4-METHYLENEDIOXY-ANILINE HCl),2,6-Dihydroxy-3,4-dimethylpyridine (2,6-DIHYDROXY-3,4DIMETHYLPYRIDINE),3,5-Diamino-2,6-dimethoxypyridine (2,6-DIMETHOXY-3,5-PYRIDINEDIAMINE),5,6-Dihydroxyindole (,DIHYDROXY-INDOLE), 4-Amino-2-aminomethylphenol(2-AMINOETHYL-p-AMINO-PHENOL HCl), 2,4-Diamino-5-methylphenetol(2,4-DIAMINO-5-METHYL-PHENETOLE HCl),2,4-Diamino-5-(2′-hydroxyethyloxy)toluene(2,4-DIAMINO-5-METHYLPHENOXYETHANOL HCl),5-Amino-4-chloro-2-methylphenol (5-AMINO-4-CHLORO-o-CRESOL),4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene(HYDROXYETHYLAMINOMETHYL-p-AMINO PHENOL HCl),4-Amino-1-hydroxy-2-methoxymethylbenzene (2-METHOXYMETHYL-p-AMINOPHENOLHCl), 1,3-Bis(N(2-Hydroxyethyl)N(4-amino-phenyl)amino)-2-propanol(HYDROXYPROPYL-BIS-(N-HYDROXY-ETHYL-p-PHENYLENEDIAMINE)HCL),6-Hydroxyindole (6-HYDROXY-INDOLE), 2,3-Indolinedione (ISATIN),3-Amino-2-methylamino-6-methoxypyridine (HC BLUE NO. 7),1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one,2-Amino-3-hydroxypyridine (2-AMINO-3-HYDROXYPYRIDINE), 5-Amino-salicylicacid, 1-Methyl-2,6-bis(2-hydroxy-ethylamino)benzene(2,6-HYDROXYETHYLAMINOTOLUENE), 4-Hydroxy-2,5,6-triaminopyrimidine(2,5,6-TRIAMINO-4-PYRIMIDINOL SULPHATE),2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine(PEG-3,2′,2′-DI-p-PHENYLENEDIAMINE), 5,6-Dihydroxyindoline(DIHYDROXYINDOLINE), N,N-Dimethyl-3-ureidoaniline(m-DIMETHYL-AMINO-PHENYLUREA), 2,4-Diamino-5-fluortoluenesulfatehydrate(4-FLUORO-6-METHYL-m-PHENYLENEDIAMINE SULPHATE) and1-Acetoxy-2-methylnaphthalene (1-HYDROXYYETHYL-4,5-DIAMINOPYRAZOLESULPHATE). These can be used in the molecular form or in the form ofperoxide-compatible salts.

The hair colouring compositions of the present invention may alsoinclude non oxidative hair dyes i.e. direct dyes which may be used aloneor in combination with the above described oxidative dyes. Suitabledirect dyes include azo or anthraquinone dyes and nitro derivatives ofthe benzene series and mixtures thereof. Such direct dyes areparticularly useful to deliver shade modification or highlights.Particularly preferred are Basic Red 51, Basic Orange 31, Basic Yellow87 and mixtures thereof.

The hair dye compositions of the present invention will generallycomprise from about 0.001% to about 10% of dyes. For examplecompositions providing low intensity dyeing such as natural blonde tolight brown hair shades generally comprise from about 0.001% to about5%, preferably from about 0.1% to about 2%, more preferably from about0.2% to about 1% by weight of dyeing composition of precursors andcouplers. Darker shades such as browns and black typically comprise from0.001% to about 10% by weight, preferably from about 0.05% to about 7%by weight, more preferably form about 1% to about 5% of precursors andcouplers.

Surfactants

The compositions according to the present invention may further compriseone or more surfactants. Surfactants suitable for use herein generallyhave a lipophilic chain length of from about 8 to about 30 carbon atomsand can be selected from anionic, nonionic, amphoteric and cationicsurfactants and mixtures thereof. Preferred surfactants includenon-ionic surfactants comprising one or more polyethyleneoxide chain,for example polyoxyethylene alkyl ethers or polyethyleneglycol fattyacid esters. Another preferred surfactants are alkyl ether sulphates oralkyl ether phosphates, where particularly preferable are alkyl etherphosphates having 1-20, preferably 1-10 and most preferably 1-5 ethyleneoxide units.

Any combination of surfactants can be used. Moreover, surfactants mayform various micelle and liquid crystalline phases in the composition.Preferably, the surfactants will form a so-called lamellar gel networkphase. The surfactants will generally be used at levels of from about0.05% to about 30% by weight of the composition, preferably of fromabout 0.1% to about 15%, more preferably of from about 0.2% to about10%.

Conditioning Agent

The compositions of the present invention may comprise or are used incombination with a composition comprising a conditioning agent.Conditioning agents suitable for use herein are selected from siliconematerials, amino silicones, fatty alcohols, polymeric resins, polyolcarboxylic acid esters, cationic polymers, cationic surfactants,insoluble oils and oil derived materials and mixtures thereof.Additional materials include mineral oils and other oils such asglycerin and sorbitol.

The conditioning agent will generally be used at levels of from about0.05% to about 20% by weight of the composition, preferably of fromabout 0.1% to about 15%, more preferably of from about 0.2% to about10%, even more preferably of from about 0.2% to about 2%.

Particularly useful conditioning materials are cationic polymers andsilicones. Conditioners of cationic polymer type may be chosen fromthose already known by those skilled in the art as improving at leastone cosmetic properties of keratin fibres treated with a cosmeticcomposition. Cationic polymers can be chosen from those comprising unitsof at least one amine group chosen from primary, secondary, tertiary andquaternary amine groups that may either form part of the main polymerchain, or be borne by a side substituent that is directly attached tothe main polymer chain.

Silicones can be selected from polyalkylsilioxane oils, linearpolydiemthylsiloxane oils containing trimethylsilyl orhydroxydimethylsiloxane endgroups, polymethylphenylsiloxanepolydimethylphenylsiloxane or polydimethyldiphenylsiloxane oils,silicone resins, organofunctional siloxanes having in their generalstructure one or a number of organofunctional group(s), the same ordifferent, attached directly to the siloxane chain. Saidorganofunctional group(s) are selected from: polyethyleneoxy and/orpolypropyleneoxy groups, (per)fluorinated groups, thiol groups,substituted or unsubstituted amino groups, carboxylate groups,hydroxylated groups, alkoxylated groups, quaternium ammonium groups,amphoteric and betain groups. The silicone can either be used as a neatfluid or in the form of an pre-formed emulsion.

Chelants

According to the present invention the compositions may comprisechelants. Chelants are well known in the art and refer to a molecule ora mixture of different molecules each capable of forming a chelate witha metal ion. Chelants are well known in the art and a non-exhaustivelist thereof can be found in A E Martell & R M Smith, Critical StabilityConstants, Vol. 1, Plenum Press, New York & London (1974) and A EMartell & R D Hancock, Metal Complexes in Aqueous Solution, PlenumPress, New York & London (1996) both incorporated herein by reference.

Examples of chelants suitable for use herein include EDDS(ethylenediaminedisuccinic acid), carboxylic acids (in particularaminocarboxylic acids), phosphonic acids (in particular aminophosphonicacids) and polyphosphoric acids (in particular linear polyphosphoricacids), their salts and derivatives.

Chelants may be incorporated into the composition of the presentinvention as stabilizers and or preservatives. In addition it has alsobeen found that chelants provide hair fibre damage benefits and thusthey may be utilized in order to further improve the hair damage profileof the present invention. Levels of chelants in the present inventionmay be as low as about 0.1%, preferably at least about about 0.25%, morepreferably about 0.5% for the most effective chelants such asdiamine-N,N′-dipolyacid and monoamine monoamide-N,N′-dipolyacid chelants(for example EDDS). Less effective chelants will be more preferably usedat levels of at least about 1%, even more preferably above about 2% byweight of the composition, depending of the efficiency of the chelant.Levels as high as about 10% can be used, but above this levelsignificant formulation issues may arise.

Opacifying Agents

Suitable opacifiers may be selected from fatty alcohols, fatty acids,fatty amide derivatives, fatty esters of ethylene glycol and fatty acidsof glycerol.

Solvents

Suitable solvents for use in the compositions of the present inventioninclude, but are not limited to, water, butoxydiglycol, propyleneglycol, alcohol (denat.), ethoxydiglycol, isopropylalcohol, hexyleneglycol, benzyl alcohol and dipropylene glycol. Finally, the compositionsaccording to the present invention are thus typically provided as anaqueous composition. The compositions of the present invention comprisefrom 10%, preferably 20%, more preferably 30%, most preferably 50% byweight of a solvent.

Method of Use

It is understood that the examples of methods of use and embodimentsdescribed herein are for illustrative purposes only and that variousmodifications or changes in light thereof will be suggested to oneskilled in the art without departing from the scope of the presentinvention.

Oxidative hair dye compositions are usually sold in kits comprising, inindividually packaged components such as separate containers, a dyecomponent (also called “dye cream” for emulsions or gels or “dye liquid”for solutions) comprising the oxidative dye, precursors and alkalizingagent which is typically ammonia in a suitable carrier, and; a hydrogenperoxide component (also called “hydrogen peroxide cream” for emulsionsor gels or “hydrogen peroxide liquid” for solutions) comprising theoxidizing agent (usually hydrogen peroxide). The consumer mixes the dyecomponent and hydrogen peroxide component together immediately beforeuse and applies it onto the hair.

Similarly, bleaching compositions are also usually sold as a kitcomprising two or three individually packaged components typically intwo or three separate containers. The first component comprises theammonium ion source (e.g. ammonia), the second component comprises theoxidizing agent and the third (optional) component comprises a secondoxidizing agent. The bleaching compositions are obtained by mixing theabove-mentioned compositions immediately before use.

After working the mixture for a few minutes (to insure uniformapplication to all of the hair), the oxidative dye composition isallowed to remain on the hair for an amount sufficient for the dyeing totake place (usually from about 2 to 60 minutes, typically about 30 to 45minutes). The consumer then rinses his/her hair thoroughly with tapwater and allows it to dry. It is observed that the hair has changedfrom its original colour to the desired colour.

When present in the oxidative dye compositions and bleachingcompositions, the optional conditioning agent can be provided in a thirdcontainer. In the latter case, all three compositions can be mixedimmediately before use and applied together, or the content of the thirdcontainer can be applied (after an optional rinse step) as apost-treatment immediately after the oxidative dye composition orbleaching composition resulting from the mixture of the othercontainers.

For hair dye compositions the polymer thickener may be comprised withinthe dye component, or the hydrogen peroxide component or bothcomponents. The resultant hair colouring or bleaching compositionsaccording to the present invention thus have a viscosity of from 1000 to60000 cPs, preferably from 2000 to 30000 cPs and most preferably from3000 to 25000 cPs. Moreover prior to mixing the hair dye component(component two) may have viscosity of less than 1000 cPs, suchcomposition is ofter referred as “thin-thin” or “liquid” colorant. Theviscosity of the resultant mixture of oxidative and dye components i)and ii) in other words the hair colouring or bleaching composition isfrom 1000 to 60000 cPs, preferably from 2000 to 30000, more preferablyform 3000 to 25000 cPs. Viscosity is measured using Brookfieldviscometers with cone and plate attachment. For viscosities in the rangeof 0-12000 cPs the Brookfield DV-11 viscometer with S42 plate is used. 2ml sample of the composition is equilibrated at 26.7° C. for threeminutes before the readings are taken at 1 rpm. For viscosities in therange of 12,000-50,000 cPs the Brookfield DV-1 viscometer with S52 plateis used. 0.5 ml sample of the composition is equilibrated for 1 minuteat 26.7° C. before the readings are taken at 1 rpm.

The present invention also includes embodiments wherein the method ofcolouring or bleaching hair comprises applying a composition comprisingat least one oxidising agent, at least one source of carbonate,carbamate, or hydrogen carbonate ions and mixtures thereof, and apolymer thickening system as defined herein free of radical scavengers,the composition having a pH of up to about 9.3, for at least about 50%of the time period the composition is applied to the hair.

According to the present invention the methods of colouring or bleachinghair also comprise embodiments whereby the composition is applied to thehair and preferably the mixture is worked for a few minutes (to insureuniform application to all of the hair). The composition is then allowedto remain on the hair in order for the colour to develop for a timeperiod of less than about 20 minutes, preferably less than about 15minutes, more preferably from about 5 minutes to about 10 minutes, mostpreferably for about 10 minutes. The consumer then rinses his/her hairthoroughly with tap water and allows it to dry and or styles the hair asusual. This method provides additional convenience to consumer bypermitting faster colouring or bleaching application.

According to an alternative embodiment of the present invention, themethod of colouring and or bleaching the hair is a sequential oxidativehair colouring or hair bleaching method comprising the steps of at leasttwo sequential oxidative hair colour or hair bleaching treatmentswherein the time period between each treatment is from 1 to 60 days,preferably from 1 to 40 days, more preferably from 1 to 28 days, evenmore preferably from 1 to 14 days and most preferably from 1 to 7 days.In such embodiments the time that the composition is retained on headmay be less than about 20 minutes and is preferably less than about 10minutes and most preferably from about 2 minutes to about 5 minutes.This method allows consumer to perform colouring or bleaching process ina way similar to conventional hair washing or conditioning process.

The kits described hereinabove are well known in the art and thecomposition in each container can be manufactured utilizing any one ofthe standard approaches. For example, polymer is added to cold waterwith strong agitation (strong agitation is not required if polymersupplied as emulsion or suspension) and then mixed for about 1 hour withreduced agitation and optional heating to provide full polymerdissolution or dispersion or swelling. This polymer premix is then mixedcold with remaining amounts of water, other optional components andoxidizing agent or a source of carbonate, carbamate or hydrogencarbonateions, thus forming first or second part of the above described bleachingor colouring kit.

The present invention may be utilized in a variety of packaging anddispensing devices. These dispensing devices can come in the form ofseparate devices which may be used independently or in combination withone another. Typically, the hair colouring or bleaching compositions arecontained within separate single or multi compartment containers so thatthe compositions can be stored separately from one another before use.The compositions are then mixed together by a mixing means and thenapplied to the consumer's hair by an application means.

The most common packaging device which can be used for the presentinvention involves storing the developer in a container such as abottle, tube, aerosol, or a sachet and separately storing the dye lotionin an additional compartment within the developer container or in aseparate container which may be identical such as a dual sachet oraesrosol systems for example or different such as a bottle and tubesystem.

The consumer may mix the developer lotion and the dye lotion by anymeans. This may simply involve the use of a mixing bowl into which thelotions are dispensed and then mixed, preferably using a mixing meanssuch as a tool. Alternatively it may involve the addition of one of thelotions into the container of the other lotion, (typically the dyelotion is added to the developer lotion), followed by manual shaking ormixing with a tool. Another system involves the perforation ordisplacement of a seal located between the separate compartments of thedye and developer lotion within a single container or sachet followed bymanual mixing within the container or in a separate and or additionalcontainer.

An example of such devices are the so called ‘twist and go’ devices.These devices allow the consumer to twist the base of a containerholding the dye which enables a communication port to open that exposesthe base of the bottle holding the dye and the top of the bottle holdingthe developer. The two components are mixed and the consumer dispensesthe product by squeezing the flexible top portion of the bottle fordispensing.

Alternatively more complex devices may be utilised, whereby the lotionsare mixed upon actuation of dispensing. An example of such as a complexsystem is a dual aerosol system e.g. bag-in-can or piston. The dye anddeveloper are stored separately in two aerosol cans within one device, apropellant being used to pressurize the contents of the can or bag incan or piston and a valve providing the control of dispensation. Whenthe consumer actuates the valve, the dye and developer are dispensedsimultaneously out of the cans and are mixed together via a static mixerjust before dispensing the product onto the hair. The ratio of the dyeand developer can be manipulated by the viscosity of the products, thecan pressure, or by altering the flow channel sizes through the valve.Additionally, the product can be foamed and delivered via a mousse form.

Another example of such a complex system utilises a dual piston screwsystem. The dye and the developer are kept in separate piston cylindersystems within the system and when the consumer actuates a button, twoscrews are rotated such that the dual pistons inside pressurize theliquid in the cylinders and thus force the products to move through amixing station and out of the nozzle for dispensing. The ratios of thedye and the developer can be manipulated by the diameter of the cylinderof the package. Additionally, an in line static mixer can be used to aidmixing and such a system can be completely disposable or completelyrefillable.

Yet another system utilises one or more manually actuated pumps. Theproduct may be premixed in a collapsible sachet. When the consumeractuates the pump, the liquid inside the pump is dispensed. As themanually actuated pump returns to the upright position it forces productfrom a collapsible sachet. Alternatively, a dual system can be installedwhereby two sachets and two pumps are used to deliver the dye and thedeveloper lotions to the hair. Alternatively, a single pump connected totwo sachets can deliver the product by incorporating the mixing pointwithin the pump. Another embodiment uses a rigid bottle and a dip tubeto connect the product to the pump system. Finally, a delaminatingbottle can be used in combination with a manually actuated pump wherethe inner layer of the bottle separates from the outer layer of thebottle which forces the contents of the bottle to be emptied.

Typically these complex systems offer the advantage of productapplication independently of the orientation of the product.

The devices described herein above can also be used in combination witha product delivery and or application tool to aid application of theproduct onto the hair. Again these devices may be of a very simplenature such as a nozzle attached to one of the containers or a separateapplicator device such as a comb or brush. Such combs and brushes can beadapted in order to achieve particular effects, whether it be quick andeven coverage or root/hairline touch up, or highlights or streaks.Alternatively, the container or one of the containers may be providedwith a comb attached to or instead of the dispensing nozzle whereby theproduct is dispensed through hollow tines and dispensing apertureslocated in the comb tines. The comb tines may be provided with single ormultiple openings along the tines to improve product application andevenness especially root to tip. Product dispensation can be achieved bymechanical pressure applied to the container for example delaminatingbottles or any of the mechanisms described hereinabove. The comb may beprovided on the container such as to facilitate easy application and maybe positioned vertically (so called verticomb) or at an angle to allowthe consumer to access all areas. All devices may be designed to haveinter-changeability, so that a range of different tools for hairapplication can be provided to the consumer.

The application devices may also include devices which assist inachieving particular effects such as highlighting such as highlightingcombs, brushes and tools, foils and highlighting caps.

Additional device technology can be used to assist in the penetration ofthe product into the hair. Examples of such technology include heatingdevices, ultraviolet light devices and ultrasound devices.

EXAMPLES

The following examples illustrate oxidative dye compositions accordingto the present invention. It is understood that the examples andembodiments described herein are for illustrative purposes only and thatvarious modifications or changes in light thereof will be suggested toone skilled in the art without departing from the scope of the presentinvention.

Examples 1-10 Mixed Compositions

Formulation Ingredient 1 2 3 4 5 6 7 8 9 10 11 Ammonium Carbonate 4.0 —2.0 — — — — 5.0 3.0 — — Ammonium Hydrogen — 1.0 — — 2.5 4.0 2.0 — — 4.01.0 Carbonate Ammonium Carbamate — 1.0 — — 2.5 4.0 2.0 — — 4.0 1.0Potassium Hydrogen — — 2.0 5.0 — — — — 1.5 — — Carbonate — — 5   — — — —— — — — Acrylates Steareth-20 8.0 — 1.0 — — — — — — — — MethacrylateCopolymer (Aculyn ® 22) Carbomer (Crabopol 980 ®) — 2.0 — — — — — — — —2.0 Acrylates Copolymer — — 4.0 — — — — — — — — (Aculyn ® 33A)PEG-150/Decyl Alcohol/ — — — 4.0 — — — — — — — SMDI Copolymer (Aculyn ®44) Succinoglycan (Rheozan ®) — — — — 1.0 — — — — — — Xanthan gum — — —— — 1.5 — — — — — Acrylates/Steareth-20 — — — — — — 2.0 — — — —Itaconate Copolymer (Structure ® 2001) Acrylates/C10-30 Alkyl — — — — —— — 2.0 — — — Acrylate Copolymer (Carbpol 2020 ®) CetylHydroxyethylcellulose — — — — — — — — 1.5 — — (Natrosol ® Plus CS)Hydroxypropyl Starch — — — — — — — — — 2.0 — Phosphate (Structure XL ®)Crodafos ® CES (Cetearyl — — 2.5 — — — — — — — — alcohol, di-cetylphosphate & ceteth-10 phosphate) Crodafos ® S2A (Ceteth-2 0.3 — — — — —— — — — phosphate) Ceteareth-25 — — — 0.5  0.25 — 0.5 0.5 0.5 0.5 —Cetyl Alcohol 0.3 — — 1.0 0.5 — 1.0 1.0 1.0 1.0 — Stearyl Alcohol 0.3 —— 1.0 0.5 — 1.0 1.0 1.0 1.0 — Sodium sulphite 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 EDTA(tetrasodium salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 p-phenylene diamine 0.8 0.6 0.1 0.8 — 0.6 0.1 0.8 — — p-amino phenol— 0.3 — 0.4 — 0.3 — 0.4 — 0.3 0.3 2,5-diaminotoluene sulphate — 0.1 0.2— — 0.1 0.2 — — 0.1 0.1 m-aminophenol 0.2 — 0.1 — 0.2 — 0.1 — 0.2 — —Resorcinol — 0.5 — 0.4 — 0.5 — 0.4 — 0.5 0.5 napthol  0.03 — 0.2 —  0.03— 0.2 —  0.03 — — 4-amino-2-hydroxy toluene — 0.2 — 0.3 — 0.2 — 0.3 —0.2 0.2 Phenyl methyl pyrazalone 0.2 — — — — 0.1 — — — — —1-hydroxyethyl-4,5-diamino 0.3 — — — — 0.2 — — — — — pyrazole sulphateBasic red 51 — 0.1 — — — — 0.2 — — — 0.1 Basic yellow 87 — 0.2 — — — —0.3 — — — 0.2 Hydrogen Peroxide 8.6 8.6 8.6 13..0 13.0  13.0  17.0 10.7  10.7  10.7  4.0 (35% active) Polyquaternium-22 — — — — 0.5 — — — —— — (Merquat ® 295) Polyquaternium-37 & — — — — 0.1 — — — 0.5 — —Mineral oil (Salcare ® SC95) Amodimethicone — — — — — — — — — 1.0 —(DCAP 6087) Propylene Glycol 4.0 3.0 3.0 4.0 3.5 3.0 4.0 4.0 3.0 3.0 3.0pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs qs Water qs qs qs qsqs qs qs qs qs qs qsThe viscosity of these compositions are within the range of from 1000 to60000 cPs.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are the scope of this invention.

1. A hair colouring or bleaching composition comprising i) at leastabout 0.2 mol/l of a source of carbonate, carbamate, hydrogencarbonateor peroxymonocarbonate ions and mixtures thereof, ii) at least oneoxidizing agent and iii) at least one polymeric thickener selected fromassociative polymers, non-associative polycarboxylic polymers, andmixtures thereof, wherein said composition has a pH of up to andincluding about 9.3 and wherein said composition is free of a source ofradical scavengers.
 2. A hair coloring composition according to claim 1,wherein said composition further comprises at least one source ofalkalizing agent, preferably ammonium ions.
 3. A hair coloringcomposition according to claim 1, wherein said composition has a pH offrom about 7.5 to about 9.3.
 4. A hair coloring composition according toclaim 1, wherein said associative polymeric thickener comprises at leastone hydrophilic unit which is a derivative of unsaturated carboxylicacid, and at least one hydrophobic unit which is selected from a C8 toC30 alkyl ester or an oxyethylenated C8 to C30 alkyl ester ofunsaturated carboxylic acid.
 5. A hair colouring or bleachingcomposition according to claim 4, wherein said unsaturated carboxylicacid is selected from acrylic acid, methacrylic acid or itaconic acid.6. A hair colouring or bleaching composition according to claim 1,wherein said associative polymer is a polyether polyurethane comprisingat least one fatty chain.
 7. A hair colouring or bleaching compositionaccording to claim 1, wherein said associative polymer is a modifiedcellulose having groups comprising at least one C8 to C30 fatty chain.8. A hair colouring or bleaching composition according to claim 1,wherein said non-associative polycarboxylic polymer is cross linkedacrylic acid homopolymer.
 9. A hair colouring or bleaching compositionaccording to claim 1, wherein said non-associative polycarboxylicpolymer is a copolymer of methacrylic acid and of C1 to C6 alkylacrylate or methacrylate or mixtures thereof.
 10. A hair colouring orbleaching kit comprising i) an individually packaged oxidizing componentcomprising at least one source of hydrogen peroxide ii) an individuallypackaged second liquid component comprising a) at least one polymericthickener selected from associative polymers, polysaccharides,non-associative polycarboxylic polymers, and mixtures thereof, and b) asource of carbonate ions, carbamate ions or hydrogencarbonate ions andmixture thereof, and c) at least about 10% by weight of a solvent,water, and wherein said kit is free of a source of radical scavengersand upon mixing said components comprises at least about 0.2 mol/l of asource of carbonate ions, carbamate ions, hydrogencarbonate ions orperoxymonocarbonate ions and mixtures thereof, except when saidpolymeric thickener is an associative polymer when said compositioncomprises at least about 0.4 mol/l of said source.
 11. A hair colouringor bleaching kit comprising i) an individually packaged liquid oxidizingcomponent comprising a) at least one source of hydrogen peroxide, and b)at least polymeric thickener selected from associative polymers,polysaccharides, non-associative polycarboxylic polymers, and mixturesthereof, and c) at least about 10% by weight of a solvent, water, ii) anindividually packaged second component comprising a source of carbonateions, carbamate ions or hydrogencarbonate ions and mixtures thereof,wherein said kit is free of a source of radical scavengers and uponmixing said components comprises at least about 0.2 mol/l of a source ofcarbonate ions, carbamate ions, hydrogencarbonate ions orperoxymonocarbonate ions and mixtures thereof, except when saidpolymeric thickener is an associative polymer when said compositioncomprises at least about 0.4 mol/l of said source.
 12. A hair colouringor bleaching composition according to claim 10, wherein saidpolysaccharide is a bio-polysaccharide.
 13. A hair colouring orbleaching composition according to claim 10, wherein said polysaccharideis a bio-polysaccharide selected from xanthan gum, gellan gum, welangum, scleroglucan, succinoglycan, or mixtures thereof.
 14. A haircolouring or bleaching composition according to claim 10, wherein saidpolysaccharide is selected from guar gum, locust bean gum or mixturesthereof.
 15. A hair colouring or bleaching composition according toclaim 10, wherein said polysaccharide is a hydroxypropyl starchphosphate.
 16. A hair colouring composition according to claim 1,wherein said composition further comprises at least one surfactantselected from anionic, nonionic, cationic or amphoteric surfactants. 17.A hair colouring composition according to claim 1, wherein saidcomposition further comprises at least one opacifier selected from fattyalcohols, fatty acids, fatty amide derivatives, fatty esters of ethyleneglycol, fatty acids of glycerol and mixtures thereof.
 18. A haircolouring or bleaching composition according to claim 1, wherein saidcomposition has a viscosity of from about 1000 to about 60000 cPs, fromabout 2000 to about 30000 cPs and most preferably from about 3000 toabout 25000 cPs.
 19. A hair colouring or bleaching composition accordingto claim 1, wherein said composition further comprises a conditioningactive.
 20. A hair colouring or bleaching composition according to claim1, wherein said composition further comprises at least one oxidative dyeprecursor and or at least one pre-formed dye.
 21. A method of colouringand or bleaching hair comprising the steps of applying a compositionaccording to claim 1 on the hair, leaving said composition on the hairfor up to about 60 minutes and subsequently rinsing said compositionfrom the hair.
 22. A method according to claim 21, wherein saidcomposition is retained on the hair for a time period of less than about20 minutes.
 23. A method of sequential oxidative hair colouring or hairbleaching comprising the steps of at least two sequential oxidative haircolour or hair bleaching treatments wherein the time period between eachtreatment is from about 1 day to about 60 days, and wherein eachtreatment comprises the steps of providing a composition according toclaim 1, applying said composition to the hair and retaining saidcomposition on the hair for a time period of less than about 20 minutesand subsequently rinsing said composition from the hair.